CN112920395B - Copolymerization type aromatic polycarbonate and preparation method thereof - Google Patents
Copolymerization type aromatic polycarbonate and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/302—General preparatory processes using carbonates and cyclic ethers
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Abstract
The invention provides a copolymerization type aromatic polycarbonate, which is formed by mixed polymerization monomers of monomers shown in a formula (1) and bisphenol monomers. The invention also provides a preparation method of the copolymerization type aromatic polycarbonate and a polycarbonate product. The copolymerization type polycarbonate provided by the invention has better heat resistance and processing performance, good refractive property and light transmission in a visible light wavelength region, obviously improved overall performance, wide raw material source, low cost, environmental protection, simple and convenient preparation process, suitability for industrial production and very wide application prospect, can be applied to a plurality of fields, particularly the optical field,
Description
Technical Field
The invention relates to the field of polycarbonate materials, in particular to a copolymerization type aromatic polycarbonate and a preparation method thereof.
Background
Polycarbonate is used as the fastest growing general engineering plastic of five engineering plastics, and is widely applied to the fields of buildings, automobiles, consumer electronics and the like at present due to the advantages of excellent impact resistance, transparency, good processability and the like. The polycarbonate can be classified into various types such as aliphatic polycarbonate, aromatic polycarbonate, aliphatic-aromatic copolymerized polycarbonate and the like according to the monomer structure, and the aliphatic and aliphatic-aromatic copolymerized polycarbonate has low mechanical properties and no practical value. Only aromatic polycarbonates based on bisphenol A have been developed very well and are produced industrially on a large scale.
On one hand, with the exhaustion of petroleum resources, the problems of polymer materials based on petrochemical monomers and adverse effects on the environment are increasingly examined, so that the preparation of polymer materials by using recyclable and environment-friendly bio-based monomers has a very broad prospect. On the other hand, the common bisphenol A polycarbonate material has bottlenecks in certain properties, such as refractive index, light transmittance, heat resistance temperature, melt fluidity, scratch resistance and the like, and can not meet the product requirements.
Therefore, there is an increasing demand for further improving the properties of aromatic polycarbonates based on bisphenol A and expanding the fields of application thereof.
Disclosure of Invention
In order to overcome the above-mentioned disadvantages of the prior art, it is an object of the present invention to provide a copolymerized aromatic polycarbonate which is remarkably improved in properties.
Another object of the present invention is to provide a process for producing a copolymerized aromatic polycarbonate.
It is a further object of the present invention to provide a polycarbonate article.
The invention provides a copolymerized aromatic polycarbonate which is formed by mixed polymerization monomers based on monomers shown in a formula (1) and bisphenol monomers,
in the formula (1), R 1 Represents hydrogen, halogen, C1-C10 alkyl, C1-C10 alkoxy, C3-C10 cycloalkyl or C6-C20 aryl; n represents an integer of 0 to 2;
in the mixed polymerization monomer, the content of the monomer represented by the formula (1) is 1-99% by mole percentage.
The invention discloses a preparation method of a copolymer type aromatic polycarbonate, which is characterized in that the existing aromatic polycarbonate is prepared based on bisphenol monomers such as bisphenol A, and the inventor of the invention finds that the copolymer type aromatic polycarbonate can be obtained by adding furan ring-containing monomers shown in formula (1) with different contents into the bisphenol monomers, and the copolymer type polycarbonate can keep good mechanical properties and can be suitable for engineering plastics due to aromaticity and rigidity of the furan ring structure. In addition, the copolymerized aromatic polycarbonate of the present invention has more excellent light transmittance (light transmittance in the visible light wavelength range > 89%) and refractive index (1.58 to 1.65) than conventional aromatic polycarbonates, and is more suitable for use in the optical field, for example, as an optical lens.
The inventor of the invention also finds that the heat distortion temperature, the melt index and the optical performance have higher correlation with the addition amount of the furan ring-containing monomer, so that various types of copolymerized polycarbonate can be obtained by adjusting the addition amount of the furan ring-containing monomer, thereby being capable of adapting to more performance requirements and expanding the types and application fields of polycarbonate products.
In the copolymerized aromatic polycarbonate provided by the present invention, the content of the furan ring-containing monomer in the mixed polymerization monomer can be selected or adjusted by those skilled in the art according to actual needs. In some preferred embodiments, the furan ring-containing monomer, i.e., the monomer represented by formula (1), may be contained in an amount of 10 to 90% by mole; in some more preferred embodiments, the content of the monomer represented by formula (1) may be 30 to 80% by mole percentage, including but not limited to 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or any combination of content intervals.
The molecular weight of the copolymerized aromatic polycarbonate provided by the present invention may be selected or adjusted by those skilled in the art according to actual needs. In some preferred embodiments, the weight average molecular weight may be 3000 to 200000; in some more preferred embodiments, the molecular weight may be 10000 to 50000; in some most preferred embodiments, the molecular weight may be 10000 to 30000.
In the copolymerized aromatic polycarbonate provided by the present invention, the monomer represented by formula (1) which is a furan ring-containing monomer may be chemically derived (for example, pure chemical synthesis), biologically derived (for example, extracted from a plant), or a combination thereof (for example, an extract obtained from a plant is chemically modified). In some preferred embodiments, R in formula (1) 1 Can represent hydrogen, chlorine, bromine or C1-C4 alkyl, n can represent an integer of 0-2. In some most preferred embodiments, the monomer represented by formula (1) may be 2, 5-dimethylolfuran (represented by formula (1'), which is derived from cellulose, can be extracted from plant straws in large quantities, and has the advantages of wide sources, low cost, environmental protection and the like. Although the most preferred furan ring-containing monomer of the present invention is 2, 5-dimethylolfuran, it is not limited thereto, and those skilled in the art will appreciate that the structure of the furan ring-containing monomer may be suitably changed according to the performance requirements of the copolymer polycarbonate, for example, when the furan ring contains an aryl substituent, the rigidity of the polymer may be suitably increased, thereby improving the mechanical properties of the polycarbonate.
In the copolymerized aromatic polycarbonate provided by the present invention, the bisphenol monomer may be any of those conventionally used in the field of aromatic polycarbonates.
In some preferred embodiments, the bisphenol monomer suitable for use in the present invention may have a structure represented by formula (2),
in the formula (2), R 2 、R 3 May each independently represent hydrogen, halogen, C1-C10 alkyl, C1-C10 alkoxy, C3-C10 cycloalkyl or C6-C20 aryl; a. b may each independently represent an integer of 0 to 4;
x may represent a single bond (i.e., represents a biphenylene group)Radicals directly joined to form biphenyl), -O-, -C (O) -, -S-, -S (O) -, -S (O) 2 -, C2-C6 linear alkylene or a structure represented by formula (3):
in the formula (3), R 4 、R 5 May independently represent hydrogen, halogen, C1-C10 alkyl, C1-C10 alkoxy, C3-C10 cycloalkyl, C6-C20 aryl or R 4 And R 5 Can be connected to form C3-C10 naphthenic base or C6-C20 aryl;
wherein the C3-C10 cycloalkyl or C6-C20 aryl is optionally substituted with one or more of the following substituents: halogen, C1-C10 alkyl or C1-C10 alkoxy.
In some more preferred embodiments, R in formula (2) 2 、R 3 May each independently represent hydrogen, chlorine, bromine or a C1-C4 alkyl group, and a and b may each independently represent an integer of 1 or 2; x may represent a structure represented by the formula (3), and in the formula (3), R 4 、R 5 Each independently represents hydrogen, chlorine, bromine or a C1-C4 alkyl group.
In other preferred embodiments, bisphenol monomers suitable for use in the present invention may include, but are not limited to, the following monomers: 2,2 '-bis- (4-hydroxyphenyl) propane (bisphenol A), 2' -bis- (4-hydroxy-3-methylphenyl) propane, 2 '-bis- (4-hydroxy-3, 5-dichlorophenyl) propane, 2' -bis- (4-hydroxy-3, 5-dibromophenyl) propane, 4 '-bis- (4-hydroxyphenyl) heptane, 4' -dihydroxybiphenyl, 3 '-dichloro-4, 4' -dihydroxybiphenyl, 9 '-bis (3-methyl-4-hydroxyphenyl) fluorene, 1' -bis- (4-hydroxyphenyl) -1-phenylethane, diphenylethane, and diphenylethane, 1,1 '-bis- (4-hydroxyphenyl) cyclohexane, 1' -bis- (4-hydroxyphenyl) -3,3', 5-trimethylcyclohexane, 1' -bis- (3-methyl-4-hydroxyphenyl) cyclohexane, 4 '-dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl sulfone, and the like.
In some most preferred embodiments, the bisphenol monomer suitable for use in the present invention may be bisphenol a.
The preparation method of the copolymerization type aromatic polycarbonate can adopt a melt transesterification method, namely, the copolymerization type aromatic polycarbonate is prepared by carrying out melt transesterification on a mixed polymerization monomer of a monomer shown as a formula (1) and a bisphenol monomer and a carbonate reagent in the presence of a catalyst.
In the preparation method provided by the invention, the carbonate reagent can be a reagent commonly used in a polycarbonate preparation process, such as diaryl carbonate. In some preferred embodiments, the carbonate reagent may be diphenyl carbonate.
In the preparation method provided by the invention, the catalyst can be a catalyst which is common in the polycarbonate preparation process, such as alkali metal hydroxide, alkali metal carbonate, quaternary ammonium salt and phosphonium compound thereof. In some preferred embodiments, the catalyst can be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium bisulfate, tetraethylammonium tetrafluoroborate, and the like, either alone or in combination; in some more preferred embodiments, the catalyst may be an alkali metal carbonate such as sodium carbonate, potassium carbonate, cesium carbonate, and the like. In some preferred embodiments, the catalyst may be used in an amount of 0.00001 to 0.025% by mole, based on the total amount of hydroxyl groups in the polymerized monomers; in some more preferred embodiments, the catalyst may be used in an amount of 0.001 to 0.01% by mole.
In some preferred embodiments, the preparation method provided by the present invention may comprise the following steps:
s1: reacting a mixed polymerization monomer of a monomer shown in a formula (1) and a bisphenol monomer with a carbonate reagent in a first reactor, wherein the temperature in the first reactor is 150-180 ℃, and the pressure is normal pressure;
s2: transferring the material in the first reactor to a second reactor to continue the reaction until the required molecular weight is reached, wherein the temperature in the second reactor is 200-350 ℃, and the pressure in the second reactor is 50 Pa-25 kPa; and
s3: and extruding and granulating the reaction product in the second reactor.
Wherein, the catalyst can be added in the step S1, and transferred to the step S2 together with the materials, or added in the step S2, or partial catalyst can be added in each step.
In some more preferred embodiments, the feed is subjected to a stepwise temperature increase and a stepwise pressure decrease in the second reactor, wherein the temperature increase and the pressure decrease may be independently uniform or non-uniform. The byproduct produced in the polymerization process is mainly phenol, the byproduct phenol can be removed from the mixture of the polymerization monomer and the product along with the gradual rise of the reaction temperature and the gradual reduction of the system pressure, the byproduct phenol can be collected in a condensation mode while being removed, and the condensation temperature can be 45-150 ℃, for example, 45-100 ℃, and also can be 45-60 ℃.
In some more preferred embodiments, the temperature of the extrusion granulation in step S3 may be 280 to 350 ℃, the byproduct phenol may be further removed by the extrusion granulation process, and the byproduct residue in the final extrusion granulated product is <100 ppm. The extrusion pelletization process of step S3 may be performed in a conventional extrusion pelletization apparatus, such as a twin-screw or single-screw extruder.
The invention also provides a polycarbonate product which is prepared by processing the copolymerization type aromatic polycarbonate in any one of the technical schemes.
The polycarbonate articles provided by the present invention may be in any form depending on the field of use, including but not limited to, shaped parts, extrudates, films, film laminates, and the like. The polycarbonate articles provided by the present invention may also be transparent, translucent, or colored articles depending on the field of use.
In the polycarbonate product provided by the invention, besides the copolymerized aromatic polycarbonate as the base material, any thermoplastic resin additive or combination thereof commonly used in the field of polycarbonate products can be added, including but not limited to a mold release agent, a flow aid, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, a dye, a pigment, a filler and the like, and the additive can be selected or adjusted by a person skilled in the art according to actual performance requirements, and the addition amount of the additive can be 0-5 wt% based on the total weight of the polycarbonate base material.
The polycarbonate product provided by the invention can be prepared according to any common processing technology in the field of polycarbonate products, and the used equipment can also be any common processing equipment in the field of polycarbonate products. For example, a polycarbonate article obtained by mixing a copolymerized aromatic polycarbonate base material with optional additives, melt-mixing in a known mixing apparatus (e.g., an internal mixer, an extruder, an injection molding machine, a twin-screw kneader, etc.), and by means of, for example, extrusion, injection molding, pelletization, etc., can be used.
Compared with the conventional aromatic polycarbonate, the copolymerization aromatic polycarbonate provided by the invention has better heat resistance and processability, also has good refractive property and light transmittance in a visible light wavelength region, and the overall performance is greatly improved. In addition, the copolymerization type polycarbonate monomer has the advantages of wide raw material source, low cost, environmental protection, simple and convenient preparation process, suitability for industrial production and very wide application prospect.
Detailed Description
Term(s)
As used herein, "C1-Cn" includes C1-C2, C1-C3, and … … C1-Cn. For example, the "C1-C10" group refers to 1-10 carbon atoms in the moiety, i.e., the group contains 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. Thus, for example, "C1-C4 alkyl" refers to an alkyl group containing 1-4 carbon atoms, i.e., the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Numerical ranges such as "1 to 6" herein refer to each integer in the given range.
The term "alkyl" as used herein, alone or in combination, refers to an optionally substituted straight chain or optionally substituted branched chain saturated aliphatic hydrocarbon. The "alkyl" herein preferably may have 1 to 10 carbon atoms, for example 1 to 8 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, 2-methyl-l-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-l-butyl, 2-methyl-3-butyl, 2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-l-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-dimethyl-l-butyl, 3-dimethyl-1-butyl, 2-methyl-l-pentyl, 2-methyl-2-pentyl, and the like, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl and hexyl, and longer alkyl groups such as heptyl and octyl, and the like. When a group as defined herein, such as "alkyl" appears in a numerical range, for example, "C1-C6 alkyl" refers to an alkyl group that may be composed of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, or 6 carbon atoms, and alkyl herein also encompasses instances where no numerical range is specified.
"alkyl" as used herein in combination refers to alkyl groups attached to other groups, for example, alkyl in alkoxy, as defined herein when used alone.
The term "alkoxy" as used herein, alone or in combination, refers to an alkyl ether group, designated "alkyl-O-". Non-limiting examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like.
The term "cycloalkyl" as used herein, alone or in combination, refers to a non-aromatic saturated carbocyclic ring, and may include a monocyclic (having one ring), a bicyclic (having two rings), or a polycyclic (having more than two rings) ring system, which may be bridged or spiro. The cycloalkyl group may have 3 to 10 ring-forming carbon atoms, for example, 3 to 6 ring-forming carbon atoms. Non-limiting examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
The term "aryl" as used herein, alone or in combination, refers to an optionally substituted aromatic hydrocarbon group having 6 to 20, such as 6 to 12 or 6 to 10 ring-forming carbon atoms, which may be a monocyclic aryl group, a bicyclic aryl group or a higher ring aryl group. The bicyclic aryl or higher aromatic group may be a monocyclic aryl fused to other independent rings, such as alicyclic or aromatic rings. Non-limiting examples of monocyclic aryl groups include phenyl; non-limiting examples of bicyclic aryl groups include naphthyl; non-limiting examples of polycyclic aryl groups include phenanthryl, anthracyl, fluorenyl, azulenyl.
The term "halogen" as used herein, alone or in combination, refers to fluorine, chlorine, bromine or iodine.
The technical solution of the present invention is further described in detail with reference to the following specific examples.
In the examples of the present invention and the comparative examples:
2, 5-Dimethylolfuran, bisphenol A, diphenyl carbonate and cesium carbonate were purchased from Shanghai Allantin Biotech Ltd.
Performance test
The method for testing the properties of the copolycarbonates synthesized in the examples of the present invention and the comparative examples is as follows:
the molecular weights and molecular weight distributions were tested by gel permeation chromatography according to GB/T27843-2011.
Heat Distortion Temperature (HDT) was tested according to ASTM D648.
Melt flow index was measured by melt indexer according to ASTM D1238.
Light transmittance the sheet having a thickness of 3mm was measured according to GB/T2410 using a Hunterlab USVIS 1839 color difference meter.
Refractive index the refractive index of a 100 μm sheet at 25 ℃ at the E wavelength was measured using an ATAGO NAR-4T Abbe refractometer.
Tensile strength, elongation at break were measured at a tensile speed of 50mm/min according to ASTM D638.
EXAMPLE 1 preparation of copolycarbonates
The molar ratio of 2, 5-dimethylolfuran to bisphenol A was 30: 70.
A5L round-bottomed flask equipped with a stirrer and a reflux condenser was sufficiently replaced with nitrogen gas to remove air therefrom, and 384g of 2, 5-dimethylolfuran, 1598g of bisphenol A, 2140g of diphenyl carbonate and 200mg of cesium carbonate were charged into the round-bottomed flask, and the mixture was heated to 160 ℃ under a nitrogen atmosphere and stirred for reaction for 30 min.
The reaction system is injected into a 5L stainless steel sealed reaction kettle which is provided with a stirrer and a byproduct condensation separator, stirring for 30min at 200 ℃ under the nitrogen atmosphere, heating to 220 ℃, reducing the pressure in the reaction kettle to 25kPa, stirring for reaction for 15min, heating to 240 ℃, reducing the pressure in the reaction kettle to 10kPa, stirring for reaction for 15min, heating to 260 ℃, reducing the pressure in the reaction kettle to 5kPa, stirring for reaction for 15min, heating to 270 ℃, reducing the pressure in the reaction kettle to 2kPa, stirring for reaction for 15min, heating to 280 ℃, reducing the pressure in the reaction kettle to 1kPa, stirring for reaction for 15min, heating to 300 ℃, reducing the pressure in the reaction kettle to 500Pa, stirring for reaction for 15min, heating to 320 ℃, reducing the pressure in the reaction kettle to 200Pa, stirring for reaction for 15min, heating to 330 ℃, reducing the pressure in the reaction kettle to 50Pa, and stirring for reaction for 60 min.
And (3) pressing the generated substances in the reaction kettle into a discharge die orifice by using nitrogen at 330 ℃, passing through a cooling water tank, and drawing to a cutting device for cutting and granulating to obtain the copolycarbonate.
EXAMPLE 2 preparation of copolycarbonates
The molar ratio of 2, 5-dimethylolfuran to bisphenol A was 40: 60.
A copolycarbonate was obtained by the method of example 1 using 513g of 2, 5-dimethylolfuran, 1370g of bisphenol A, 2140g of diphenyl carbonate, and 200mg of cesium carbonate.
EXAMPLE 3 preparation of copolycarbonates
The molar ratio of 2, 5-dimethylolfuran to bisphenol A was 50: 50.
A copolycarbonate was obtained by the method of example 1 using 641g of 2, 5-dimethylolfuran, 1142g of bisphenol A, 2140g of diphenyl carbonate, and 200mg of cesium carbonate.
EXAMPLE 4 preparation of copolycarbonates
The molar ratio of 2, 5-dimethylolfuran to bisphenol A was 60: 40.
A copolycarbonate was obtained by the method of example 1 using 769g of 2, 5-dimethylolfuran, 913g of bisphenol A, 2140g of diphenyl carbonate, and 200mg of cesium carbonate.
EXAMPLE 5 preparation of copolycarbonates
The molar ratio of 2, 5-dimethylolfuran to bisphenol A was 70: 30.
A copolycarbonate was obtained by the method of example 1 using 897g of 2, 5-dimethylolfuran, 685g of bisphenol A, 2140g of diphenyl carbonate, and 200mg of cesium carbonate.
EXAMPLE 6 preparation of copolycarbonates
The molar ratio of 2, 5-dimethylolfuran to bisphenol A was 80: 20.
A copolycarbonate was obtained by the method of example 1 using 1025g of 2, 5-dimethylolfuran, 457g of bisphenol A, 2140g of diphenyl carbonate, and 200mg of cesium carbonate.
Comparative example 1
Preparation of bisphenol A polycarbonate
A copolycarbonate was obtained by the method of example 1 using 0g of 2, 5-dimethylolfuran, 2283g of bisphenol A, 2140g of diphenyl carbonate, and 200mg of cesium carbonate.
The results of the performance tests of the polycarbonates prepared in examples 1 to 6 and comparative example 1 are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the copolycarbonates obtained in examples 1 to 6 had comparable tensile strength and elongation at break to those of comparative example 1, and it was found that the addition of 2, 5-dimethylolfuran did not affect the mechanical properties of the polycarbonate.
In examples 1 to 6, the heat distortion temperature and melt index of the obtained polycarbonate product were significantly increased with the increase of the content of 2, 5-dimethylolfuran in the polymerization monomer, and it was found that the heat resistance and processability were significantly improved, and the adjustment was conveniently made in accordance with the content of 2, 5-dimethylolfuran.
In addition, the polycarbonate products of examples 1-6 are also superior to comparative example 1 in both light transmittance and refractive index, especially refractive index, indicating that the polycarbonate products of the present invention are more suitable for use in the optical field, such as optical lenses.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (11)
1. A copolymerized aromatic polycarbonate which is formed by mixing and polymerizing monomers based on a monomer represented by the formula (1) and a bisphenol monomer,
in the formula (1), R 1 Represents hydrogen, halogen, C1-C10 alkyl, C1-C10 alkoxy, C3-C10 cycloalkyl or C6-C20 aryl; n represents an integer of 0 to 2;
in the mixed polymerization monomer, the content of the monomer shown in the formula (1) is 10-90% by mol percent;
the bisphenol monomer is 2,2 '-bis- (4-hydroxyphenyl) propane, 2' -bis- (4-hydroxy-3-methylphenyl) propane, 2 '-bis- (4-hydroxy-3, 5-dichlorophenyl) propane or 2,2' -bis- (4-hydroxy-3, 5-dibromophenyl) propane.
2. The copolymerized aromatic polycarbonate of claim 1, wherein the monomer represented by the formula (1) is contained in the mixed polymerization monomers in an amount of 30 to 80% by mole.
3. The copolymerized aromatic polycarbonate of claim 1 or 2, wherein the polycarbonate has a weight average molecular weight of 3000 to 200000.
4. The copolymerized aromatic polycarbonate of claim 3, wherein the polycarbonate has a weight average molecular weight of 10000 to 50000.
5. The copolymerized aromatic polycarbonate of claim 4, wherein the polycarbonate has a weight average molecular weight of 10000 to 30000.
6. The copolymerized aromatic polycarbonate of claim 1 or 2, wherein the monomer represented by formula (1) is 2, 5-dimethylolfuran.
7. The copolymerized aromatic polycarbonate of claim 3, wherein the monomer represented by formula (1) is 2, 5-dimethylolfuran.
8. The method of producing a copolymerized aromatic polycarbonate of any of claims 1 to 7, wherein the copolymerized aromatic polycarbonate is produced by melt transesterification of a mixed polymerization monomer of the monomer represented by formula (1) and a bisphenol monomer and a carbonate reagent in the presence of a catalyst.
9. The method of claim 8, wherein the carbonate reagent is diphenyl carbonate.
10. The method of claim 8 or 9, wherein the catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium bisulfate, and tetraethylammonium tetrafluoroborate.
11. A polycarbonate article produced by processing the aromatic copolymer polycarbonate of any one of claims 1 to 7.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5491180A (en) * | 1994-08-17 | 1996-02-13 | Kao Corporation | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
| FR3072388A1 (en) * | 2017-10-16 | 2019-04-19 | Roquette Freres | CROSS-LINKABLE PULVERULENT COATING COMPOSITION |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5491180A (en) * | 1994-08-17 | 1996-02-13 | Kao Corporation | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
| FR3072388A1 (en) * | 2017-10-16 | 2019-04-19 | Roquette Freres | CROSS-LINKABLE PULVERULENT COATING COMPOSITION |
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